Detergent composition with improved bleaching efficiency



EXAM in r. n

3,211,658 Patented Oct. 12, 1965 1 2 2 1 6 In the practice of this invention, the term suostantially 1 58 dry denotes a flowable particulate apparently dry solid DETERGENT COMPOSITION WITH IMPROVED BLEACHING EFFICIENCY Jean Lucien Hirtz, Suresnes, and Gilles Noiriel, Puteaux,

containing up to 12 to 16% moisture and preferably 12 /215 /2% moisture.

France, i by meme assignments, to Colgate. 5 The dissociation constants indicated above are deter- Polmolive Company, New York, N.Y., a corporation mined at the conditions most generally accepted in the of Delaware literature for determinations of this kind. These condi- No l )rawing. Filed Mar 12, 1962, Ser. No. 179,197 tions are a temperature of from 20 to 30 degrees C., and

Claims Priority, PP g i 1961, an ionic strength of 0.1, using an electrolyte consisting 9 of potassium chloride.

6 Chums (CL 25%) 10 It is to be understood that these conditions of measure- The present invention relates to an improved method ment are not those encountered during the washing, but of laundering at the boil and to detergent compositions represent a Standard for indicating and determining the the fo having h d bl hi fli i appropriate dissociation constants which will enable the Detergent compositions previously proposed for skilled worker to choose the desired sequestering agents laundering t h b il are complex mixtures comprising for the detergent compositions of this invention. In this one or several synthetic detergents, such as an alkyl aryl regard, it Should he noted that the Optimum concentration sulfonate, various mineral salts (most often alkaline ph of copper ions beyond which the speed of decomposition h d Substances f preventing d i i of of the perborate, which increases with the concentration soil on washed goods once the soil is removed therefrom. of pp ions, becomes too r pi or good bleaching is In addition, it has also been proposed that h compo .00001 to .0001 molar. Slight changes in the concentrasitions contain optical blueing agents, perfumes, antition of PP ions below above Optimum (which is corrosion agents and the like. On some occasions, soap about .000001 to .00001 molar) will result in a decrease is proposed for use in place of the above-indicated synin the bleaching Power of the PeThOTate- In Praetiee it h i d t was heretofore impossible to obtain this optimum con-4 However, it has long been recognized that under normal eenti'atien- PY i e sequestering agents essential i washing conditions such detergent mixtures are not ald the e0inP$1tin$ of this invention f rm a metal buffer ways efiective to remove all soils from laundry. This is with the Water-Soluble PP Salt, whieh maintains the 5 because some soils are stains caused by various coloring amount of free pp Present in the Washing medium at matter which'are fixed on textile fibers by a mechanism a value PP i E to h conducive to maximum 5 similar to dyeing. Unfortunately this coloring is very leaching etheleney irrespective of pp additions Which often encountered as, for example, in the stains caused are far in excess of that necessary in achieve that by wine, tea, coffee, cocoa, fruit, lipstick and the like. mun! yaine- In order to remove these dye-like stains, it is generally 7 The eieet1n of an Organic detergent use in t necessary to perform an oxidizing ti eatment. For this eofnpesltions of the Present invention is not narrowly reason, a large number of detergent compositions contentleaih detergent y be y Water-Soluble anionic, tain, in addition to the previously mentioned components, or non'lenic e d having detergent P P a certain amount of a persalt bleaching agent such as ampies of Suitable anionic detergents which fall t n a water-soluble perborate. The perborate most generthe P of the Invention include the Soaps, Such as the ally employed is sodium perborate, in amounts of between 40 water-soluble salts of higher fatty acids or rosin acids 5 and 30% by weight f the detergent mixture such as may be derived from fats, oils and waxes of However, the perborate not only oxidizes the coloring ammal, vegetable or marine Origin. s the sodium soaps matter contained in the material to be laundered, but of tallow, grease, coconut oil, tall oil and mixtures therel decomposes thereby releasing gaseous oxygem This of; and the sulfated and sulfonated synthetic detergents, liberation of gaseous oxygen is highly wasteful and re- 40 Particularly those having about 3 to 26 and Preferably sults in a loss of a substantial amount of perborate. Since about 12 to 22 carbon toms to the molecule. the latter is an expensive material, this loss is highly As examples P Suitable Synthetic anionic detergents significant. Moreover, heavy metals, even those conmay he cited the hlghei alkyl InOnOnnelear a tained as impurities in water or in washing containers, mahc shlfohates such as the higher aikyi benzene catalyze the decomposition f the perborate fonates containing from 10 to 16 carbon atoms in the In order to overcome this undesirable catalytic action, alkyl Emu? the sodium Salts of p py heXyi, it has been proposed to include certain strong sequestering hctylt holly}, decyl, dodecyl or kery1 benzene suitonates) agents such as ethylene diamine tetra-acetic acid (EDTA) and the higher alkyl toluene xylene and P n t" or its Salts, and di ethy1ene mamine penta acetic acid fonates; alkyl naphthalene sulfonates, such as sodium d1- (DTPA) or its salts, in detergent compositions contain- Sohropyl naphthalene shlfhhatei ammonium dlaniyl m sodium perborate However, in the course of naphthalene sulfonate, and sodium dmonyl naphalene sulresearch, it has been discovered that although the presence fohate; sulfated ahphahc aicohols h as sodium dodecyl of these sequestering agents diminishes catalytic decom and hexadecyl sulfates, triethanolamtne dodecyl sulfate, position of the perborate, such presence also weakens the h sohmm oleyl Sulfate; Sulfated. and shlfohated fatty bleaching power thereof oils, acids or esters, such as the sodium salts of sulfonated In accordance with the present invention, a stable, sub- Castor 011 and sulfated red O11; sulfaied hydioxyamldes stantially dry perborate-containing detergent composition such as Sulfated hydrohy'ethyl lauraimde; Sodmm h of comprises a water-soluble organic detergent, a waterg fihs ggg i gzfi 32 1 2 33 2,? sulfosuccmate; Soluble perborate a water-soluble? morgamc copper i Also included within the ambit of the invention are the and a sequestering agent Stable m the hresehce of sald sulfuric acid esters of polyhydric alcohols incompletely herhorath h forms a complex whh copher esterified with higher fatty acids, e.g. coconut oil monoing a dissociation constant the common logar1thm of glyceride munosulfate, tanow diglyceride monosulfate; which 15 between about and Said copper Salt and the hydroxy sulfonated higher fatty acid esters such and sequestering agent bcing Present in amounts sufiicient as the higher fatty acid esters of low molecular weight to enhance the bleaching action of the perborate at the boil.

alkylol sulfonic acids, e.g. oleic acid ester of isethionic acid.

Suitable non-ionic surface active agents are well known to the art and include such agents as the condensation products of alkyl phenols with ethylene oxide, e.g. the reaction product of isoctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; condensation products of tall oil with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate; the condensation products of polypropylene glycol with ethylene oxide; and the higher fatty acid alkylolamides, eg the diethanolamide of coconut oil fatty acids.

The concentration of detergent in the inventive com positions will generally range from 4 to by weight. Substantial amounts of compatible builder materials will also be usually present, i.e. of the order of between about 40 to 90% by Weight of the detergent composition. Among the builders particularly suitable for the compositions of this invention are water soluble inorganic salts such as sodium sulfate, sodium chloride, sodium tripolyphosphates, sodium pyroand ortho-phosphates, sodium carbonate and the like.

The perborate bleaching agent preferably employed in the compositions of this invention is sodium perborate and more particularly sodium perborate tetrahydrate, though it will be understood that other perborates can be employed as the bleach. Similarly although copper sulfate is preferably employed as the catalytic agent, any water-soluble copper salt will serve, as for example, the highly soluble nitrate or acetate salts.

Illustrative of the sequestering agents which will form a complex with copper having the essential dissociation constants are methylaminodiacetic acid, aminotriacetic acid and hydroxyethylaminodiacetic acid. These agents form complexes with copper having the following dissociation constants expressed in (logarithms).

Dissociation constant Agent: of copper complex Methylaminodiacetic acid 11.09 Aminotriacetic acid 12.68 Hydroxyethylaminodiacetic acid 11.90

Among these sequestering agents the most preferred is aminotriacetic acid (ATA). Substances such as leucine and asparagine, which form copper complexes having dissociation constants within the range indicated for this invention, are not satisfactory because of their instability in the presence of the perborate.

It is to be understood that the pH of the present detergent compositions will normally be in the range from 8-11.5 and that, therefore, the sequestering agents are probably present in the detergent composition as salts. It is to be also understood that strong sequestering agents such as EDTA cannot be effectively employed in the compositions of this invention. This is because EDTA forms a complex with copper having a dissociation constant of 18.5 which is too high, and hence unsatisfactory, for the practice of this invention.

As a consequence of the improved bleaching efiiciency at the boil of the perborate in a composition according to the present invention, the content of perborate can be diminished relatively to that of comparable detergent compositions containing strong sequestering agents such as EDTA. The amounts of perborate can be reduced to 5% by weight of the entire composition without experiencing any diminution in bleaching effect in comparison to comparable compositions which contain 10% perborate but lack the instant combination of copper salt and indicated sequestrant. Similarly, compositions containing 10% perborate in combination with 0.2% EDTA by weight without copper salt offer no greater bleaching efficiency than compositions containing 3% perborate, 0.4% ATA and 0.02% by weight anhydrous copper sulfate.

In order to obtain the best results, the amount of copper salt in the detergent composition of this invention must be such that the composition contains from about 30 to about 300 p.p.m. (parts per million) of copper and preferably from 40 to p.p.m. The associated amount of sequestering agent should be such'that about 3 to 15 molecules and preferably 10 to 13, thereof, should be present per atom of copper in the detergent composition.

The compositions of this invention can be prepared in any suitable manner such as, e.g., by spray drying the detergent mixture, the mineral salts, and the copper salt, and then adding, by dry mixing, the perborate and the sequestering agent as well as those constituent which could be sensitive to heat, such as perfume.

The bleaching efficiency percentage of the compositions of this invention is determined as follows:

Samples of cotton fabric are dyed by means of an oxidizible dye and washed with a bleach-free organic detergent until the complete removal of the excess of dye. These dyed fabrics, having a reflectance on a Hunter colorimeter in the range of 20, are washed with a detergent composition containing an organic detergent and a persalt, in glass beakers, for the time intervals and at temperatures used in a normal washing at the boil. The persalt partly oxidizes the dye and after washing, the fabric is lighter than at the start.

The reflectance of the fabric is measured by means of a Hunter photocolorimiter equipped with a green filter. For convenience the reflectance may be represented as BD before dyeing, BW before washing, and AW after washing. The bleaching efiiciency, in percent, is then 100 (AW-BW) divided by (BDBW).

The following formulations are representative of the compositions of this invention:

Water-soluble organic anionic or nonionic detergent (Synthetic detergent, soap or their mixtures) 4 to 40%. Water-soluble inorganic salts 40 to Perborate, especially sodium 3 to 20%. Water-soluble copper salt in an amount corresponding in relation to the entire composition of 30 to 300 p.p.m. of Cu (003% to .03%). sequestering agent which forms a copper complex having a dissociation constant the common logarithm of which is between -11 and 15, in an amount corresponding for each atom of Cu, of 3 to 15 molecules. Perfume, coloring matter, blueing agent 0 to 1%.

The following examples are given further to illustrate the invention. They are not to be regarded as limiting, the claims being the sole limitation. All amounts and percentages in the specification and in the examples are by weight unless otherwise indicated.

EXAMPLE 1 A basic detergent composition is made of the following formulation:

Percent by weight Sodium dodecylbenzene sulfonate 22 Sodium tripolyphosphate 30 Monoethanolamide of coconut oil fatty acid 2.5 Sodium silicate 7 Magnesium silicate l Hydrated sodium perborate 10 Fluorescent dye, perfume, sodium sulfate, and moisture, balance to Washing solutions are prepared by dissolving 12.5 grams or 5 grams per liter of the above basic detergent composition in aqueous washing mediums. Washing is then carried out at the boil and the results noted using each solution. Other washing solutions are prepared in like manner but with the difference that methylaminodiacetic acid, hydroxyethylaminodiacetic acid or aminotriaoetic acid sequestrants are separately added to the basic detergent compositions at concentrations of 0.2% by weight of the basic detergent composition.

To separate portions of the respective washing solutions 0, l, 2, 3, 4 or 5 p.p.m. of copper ions are added, in the form of copper sulfate, and washing is thereupon carried out. The obtained results are indicated in Table I below. In this table maximum bleaching attained for each of the formulas is indicated as well as the length of the bleaching plateau. This plateau is defined as being the interval of concentrations in copper ions (as p.pm. in the washing solution) for which the maximum bleaching eflicieney is not reduced by more than of the maximum value.

6 EXAMPLE 4 The following formulation also exhibits enhanced bleaching action at the boil.

Condensation product of tall oil with 15 moles of ethylene oxide 4%. Sodium tripolyphosphate Sodium silicate 7%. Sodium perborate tetrahydrate 10% atom of Cu of 12 molecules. Fluorescent dye, perfume, sodium sulfate and moisture Balance to 100%.

EXAMPLE 5 Another detergent composition of the subject invention is made of the following formulation. It also exhibits enhanced bleaching action at the boil.

Table I 5. g./l. of detergent 12.5 g./l. of detergent Dissociation composition composition constant of sequestering agent the copper complex Maximum Length of Maximum Length of (log.) bleaching the bleachbleaching the bleachefiieiency, ing eflicieney, ing

percent plateau percent p1ateau" None 39 0. 5 61 0. 75 Methylaminodiaeetic acid 11.1 53 3. 8 64. 5 5. 0 Hydroxyethylaminodiaeetic acidll. 9 53 3. 8 73 4. 9 Aminotriaoetic acid 12.8 60 4. 7 73 4. 6

EXAMPLE 2 Sodium dodecylbenzene sulfonate 8%. To separate portions of the basic detergent formula- 40 g i salt of sulfated lauryl alco 87 tion indicated in Example 1, there are added 0.2% by M o 15"";"75'"; weight EDTA or 0.4% ATA and 0.02% anhydrous copper g #3" e 3 7 sulfate. To a similar third basic formulation but having ty 'm-"i a perborate concentration of only 6% by Weight there iS i yp 05p g also added 0.4% ATA and 0.02% of copper sulfate. P? Y rate Sodium silicate 7%.

These formulations are then dissolved as in Example 1, to form washing solutions. The bleaching efliciency of each solution is observed and tabulated in Table 11 be low.

Table II Compositions: Bleaching efiiciency, percent Basic composition containing EDTA and 10% perborate 29 Basic composition containing ATA, copper and 10% perborate 4 Basic composition containing ATA, copper and 6% perborate 36 EXAMPLE 3 Another detergent composition of the subject invention is made of the following formulation. It exhibits highly efficient bleaching action when used at the boil.

Sodium tetrapropylbenzene sulfonate 31%. Sodium tripolyphosphate 35%. Sodium silicate 5.8%. Sodium perborate tetrahydrate 10%.

Copper sulfate in an amount corre- Copper acetate in an amount corresponding in relation to the entire composition of p.pm. of Cu. Hydroxyethylaminodiacetic acid in an amount corresponding for each atom of Cu of l0 molecules. Fluorescent dye, perfume, sodium sulfate and moisture Balance to EXAMPLE 6 The following formulation also exhibits enhanced bleaching action at the boil.

Percent Condensation product of oleic acid with ethylene It is to be understood that the invention is not limited to the specific embodiments described above. Various modifications can be made in the process and in the inventive preparations without departing from the spirit or scope of the invention.

x .1. V I:

What is claimed is:

1. A stable, substantially dry, perborate-containing detergent composition effective for washing at the boil, consisting essentially of by weight from about 4 to 40% of a member selected from the group consisting of water-soluble, synthetic, non-soap anionic and nonionic organic detergents, from about 3 to about 20% watersoluble inorganic perborate, from about 40 to about 90% water-soluble inorganic alkali metal non-oxidizing builder salts, a water-soluble inorganic copper salt, and a sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid, and bydroxyethylaminodiaeetic acid, the copper salt being present in amount sufficient to produce a copper atom concentration of from about 30 to 300 parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 3 to 15 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.

2. A composition according to claim 1 in which the perborate is sodium perborate tetrahydrate and the water-soluble copper salt is copper sulfate.

3. A composition according to claim 1 in which the detergent is a sodium salt of an alkyl aryl sulfonate containing from 10 to 16 carbon atoms in the alkyl group.

4. A composition according to claim 1 in which the concentration of copper is from 40 to 80 parts per million parts by weight of the detergent composition, and the sequestering agent is present in amount such that 10 to 13 molecules thereof are contained in the detergent composition per atom of copper.

5. A stable substantially dry perborate-containing detergent composition effective for washing at the boil, consisting essentially of by weight from 4 to 40% of a sodium salt of a higher alkyl benzene sulfonate containing from 10 to 16 carbon atoms in the alkyl group, from 3 to 20% sodium perborate tetrahydrate, from 40 to 90% water-soluble inorganic alkali metal non-oxidizing builder salts, copper sulfate and a sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid, and hydroxyethylaminodiacetic acid, the copper salt being present in amount suflicient to produce a copper atom concentration of from 40 to parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 10 to 13 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.

6. A stable substantially dry perborate-containing detergent composition effective for washing at the boil, consisting essentially of by weight about 22% sodium dodecylbenzene sulfonate, about 30% sodium tripolyphosphate, about 2.5% monoethanolamide of coconut oil fatty acid, about 7% sodium silicate, about 1% magnesium silicate, about 10% hydrated sodium perborate, copper sulfate and sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid and hydroxyethylaminodiacetic acid, the copper sulfate being present in amount sufficient to produce a copper atom concentration of from 40 to 80 parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 10 to 13 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.

References Cited by the Examiner UNITED STATES PATENTS 2,240,957 5/41 Munz 25299 XR 2,498,344 2/50 Rider et al. 252-99 XR 2,542,385 2/51 Ayo et al. 252-89 2,975,139 3/61 Kaufimann et al. 252-99 3,156,654 11/64 Konecny et al. 252

FOREIGN PATENTS 765,750 1/57 Great Britain.

OTHER REFERENCES Sequestrene, Geigy Ind. Chemical, 1952, page 5.

JULIUS GREENWALD, Primary Examiner.

ALBERT T. MEYERS, Examiner. 

1. A STABLE, SUBSTANTIALLY DRY, PERBORATE-CONTAINING DETERGENT COMPOSITON EFFECTIVE FOR WASHING AT THE BOIL, CONSISTING ESSENTIALLY OF BY WEIGHT FROM ABOUT 4 TO 40% OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE, SYNTHETIC,NON-SOUP ANIONIC AND NONIONIC ORGANIC DETERGENTS, FROM ABOUT 3 TO ABOUT 20% WATERSOLUBLE INORGANIC PERBORATE, FROM ABOUT 40 TO ABOUT 90% WATER-SOLUBLE INORGANIC ALKALI METAL NON-OXIDIZING BUILDER SALTS, A WATER-SOLUBLE INORGANIC COPPER SALT, AND A SEQUESTERING AGENT SELECTED FROM THE GROUP CONSISTING OF METHYLAMINODIACETIC ACID, AMINOTRICTIC ACID, AND HYDROXYETHYLAMINODIACETIC ACID, THE COPPER SALT BEING PRESENT IN AMOUNT SUFFICIENT TO PRODUCE A COPPER ATOM CONCENTRATION OF FROM ABOUT 30 TO 300 PARTS PER MILLION PARTS BY WEIGHT OF THE DETERGENT COMPOSITION, AND THE SEQUESTERING AGENT BEIG PRESENT IN AMOUNT SUCH THAT 3 TO 15 MOLECULES THEREOF ARE CONTAINED IN THE DETERGENT COMPOSITION PER ATOM OF COPPER, SAID AMOUNTS OF COPPER SALT AND SEQUESTERING AGENT ENHANCING THE BLEACHING ACTION OF THE PERBORATE AT THE BOIL. 